POLYMERIZATION OF ETHYLENE IN THE PRESENCE
293
The complexes were synthesized according to the Yield 0.61 g (87%). Found, %: C, 61.13; H, 7.36; N,
following procedure:
Complex 1. A solution of ligand 1L (0.32 g, Cl N O TiZr (704), %: C, 61.16; H, 7.41; N, 3.96; Cl,
H
3
.92; Cl, 9.97; Zr, 12.85. Calculated for C36
52-
2
2
2
1
mmol) in toluene (10 mL) was placed into a
−1
1
1
0.03; Zr, 12.90. IR spectrum (ν
(Nujol), cm ):
max
Schlenk tube filled with argon, 0.23 g (1 mmol) of
1
623, 1589, 1562. H NMR spectrum (CDCl , ppm):
.32–1.40 (m, 36H), 3.31 (s, 2H), 3.62 (m, 6H), 6.99–
3
TiCl (Oi-Pr) was added upon stirring, and it was
2
2
1
stirred for 20 h. Then the solution was evaporated in
vacuum, and the obtained crystalline substance was
recrystallized from a toluene–hexane mixture (1 : 1).
7.30 (m, 4H), 8.11 (s, 2H, CH=N).
Complex 5. A solution of ligand 2L (0.55 g,
1 mmol) in toluene (10 mL) was placed into a Schlenk
tube filled with argon, 0.12 g (1 mmol) of VOCl was
added upon stirring, and it was stirred for 20 h. Then
the solution was evaporated in vacuum, and the
obtained crystalline substance was recrystallized from
hexane. Yield 0.56 (84%). Found, %: C, 66.75; H,
2
5
Yield 0.38 g (87%). T 250–300°C. [a] +390 (c =
m
D
0.033, CHCl ). Found, %: C, 54.67; H, 4.53; N, 6.32;
3
3
Cl, 16.10; Ti, 10.86. Calculated for C H Cl N O Ti
20
20
2
2
2
(
1
438), %: C, 54.70; H, 4.59; N, 6.38; Cl, 16.15; Ti,
0.90. IR spectrum (ν
−1
(Nujol), cm ): 1618 s,
max
1
1
583 m, 1560 m. H NMR spectrum (CDCl , ppm):
3
1.72–1.88 (m, 8H), 3.32–3.41 (t, 2H), 6.98–7.40 (br,
8
.05; N, 4.28; Cl, 5.42; V, 7.80. Calculated for C H
36 52-
13
8
H), 8.14 (s, 2H, CH=N). C NMR spectrum
ClN O V (646), %: C, 66.81; H, 8.10; N, 4.33; Cl,
.48; V, 7.87. IR spectrum (ν (Nujol), cm ): 1628,
583, 1560, 995. H NMR spectrum (CDCl , ppm):
2
3
(
CDC1 ): 24.1, 28.4, 29.8, 35.4, 122.2, 126.2, 133.5,
3
−1
5
1
133.7, 137.6, 160.2, 161.7.
max
1
Complex 2. A solution of ligand 2L (0.55 g, 1
3
mmol) in toluene (10 mL) was placed into a Schlenk 1.49–1.52 (m, 36H), 3.42 (s, 2H), 3.81 (m, 6H), 6.65–
tube filled with argon, 0.23 g (1 mmol) of TiCl (Oi- 7.17 (m, 4H), 8.11 (s, 2H, CH=N).
2
Pr) was added upon stirring, and it was stirred for
2
The process was performed in toluene in a 100-mL
2
0 h. Then the solution was evaporated in vacuum,
glass reactor at an ethylene pressure of 2 atm. The
and the obtained crystalline substance was recrystal-
lized from hexane. Yield 0.56 (84%). Found, %: C,
reactor was preliminarily evacuated for 1 h at 90°C (up
−3
to 5 × 10 atm), cooled down to ~20°C, and 60 mL of
6
5.10; H, 7.85; N, 4.17; Cl, 10.65; Ti, 7.19. Calculated
−4
for C H Cl N O Ti (662), %: C, 65.16; H, 7.90; N, heptane, 6 × 10 mol of triisobutylaluminum (TIBA,
36
52
2
2
2
4.22; Cl, 10.69; Ti, 7.21. IR spectrum (ν
(Nujol), a sanifying and activating additive), and ethylene were
max
−1
1
added upon stirring. The polymerization was initiated
5–20 min after the completion of the preparatory
cm ): 1618, 1583, 1560. H NMR spectrum (CDCl ,
3
1
ppm): 1.29–1.47 (m, 36H), 3.36 (s, 2H), 3.78 (m,
operations by breaking a glass ampoule with the pre-
liminarily prepared catalyst in the reactor, and it was
terminated by introducing a 10% solution of HCl in
ethanol into the reactor. The polymer product was fil-
tered off, repeatedly rinsed with water and alcohol,
and dried in vacuum at 50–60°C to a constant weight.
6H), 6.90–7.21 (m, 4H), 8.15 (s, 2H, CH=N).
Complex 3. A solution of ligand 3L (0.47 g,
mmol) in toluene (10 mL) was placed into a Schlenk
1
tube filled with argon, 0.23 g (1 mmol) of TiCl (Oi-
2
Pr) was added upon stirring, and it was stirred for
2
2
0 h. Then the solution was evaporated in vacuum,
and the obtained crystalline substance was recrystal-
lized from toluene. Yield 0.41 (69%). Found, %: C,
The molecular weight characteristics (M , M ,
w
n
MWD) of PE were measured for the solutions of the
polymers in 1,2-dichlorobenzene at 135°C via gel per-
meating chromatography on a Waters 150-C instru-
ment equipped with a linear HT-μ-styragel column.
6
4.92; H, 4.70; N, 4.70; Cl, 11.91; Ti, 8.03. Calculated
for C H Cl N O Ti (590), %: C, 64.99; H, 4.77; N,
32
28
2
2
2
4.74; Cl, 11.99; Ti, 8.09. IR spectrum (ν
(Nujol),
max
−1
1
cm ): 1620, 490, 547. H NMR spectrum (CDCl ,
3
ppm): 2.43–2.55 (m, 8H), 3.41–3.59 (m, 2H), 7.36–
7
.98 (m, 18H, Ar).
Complex 4. A solution of ligand 2L (0.55 g,
mmol) in toluene (10 mL) was placed into a Schlenk
RESULTS AND DISCUSSION
The ligands used in the study were obtained by the
interaction of salicylic aldehydes with cyclohexanedi-
amine [11–14]. The complexes presented in Scheme 1
1
tube filled with argon, 0.38 g (1 mmol) of ZrCl ·
4
2
THF was added upon stirring, and it was stirred for
2
4 h upon heating. Then the solution was evaporated were obtained by the interaction of L,L-bis(sali-
in vacuum, and the obtained crystalline substance was cylidene)cyclohexanediamines with titanium(IV), zir-
recrystallized from a toluene–hexane (2 : 1) mixture. conium(IV), and vanadium(V) halides.
PETROLEUM CHEMISTRY Vol. 60 No. 3 2020